Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
  • C09B57/004—Diketopyrrolopyrrole dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0004—Coated particulate pigments or dyes
  • C09B67/0005—Coated particulate pigments or dyes the pigments being nanoparticles
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/41—Organic pigments; Organic dyes

Definitions

• Pigment dispersants are pigments substituted with groups having specific activity.
• the pigment dispersants are usually added subsequently to the pigments in order to facilitate the dispersion in the application media, in particular in paints, printing inks and inks, and to improve the theological and coloristic properties of the pigments. As a result, for example, the color strength, the transparency and the gloss can be increased in many applications.
• WO 01/04215 discloses finely divided diketopyrrolopyrrole pigments which are characterized by a particularly narrow particle size distribution coupled with high crystallinity and a specific absorption characteristic.
• Such a Cl. Pigment Red 254 can be obtained by subjecting a crude pigment initially stirred with an inorganic salt dry at least 80 0 C, and then a kneading process with inorganic salts in the presence of organic solvents is exposed.
• EP-A-0 962 499 describes a synthesis of diketopyrrolopyrrole pigments wherein the ring closure reaction is carried out in the presence of crystal growth inhibitors.
• the object was to develop a process from which DPP pigments without aftertreatment, such as grinding or salt kneading, are obtained from the synthesis, which have high color strength, high transparency and low viscosity and are particularly suitable for color filter applications or highly transparent colorations.
• the invention relates to a process for the direct preparation of finely divided 1, 4-diketopyrrolo [3,4-c] pyrroles of the formula (I), characterized by a maximum of the frequency distribution of the crystalline particles (mode of distribution) between 30 and 130 nm, preferably between 40 and 125 nm,
• R 1a , R 1b , R 2a and R 2b independently of one another are hydrogen, halogen, such as, for example, chlorine or bromine, C 1 -C 4 -alkyl, such as, for example, methyl, ethyl or tert-butyl, C 1 -C 4 -alkoxy, such as for example, methoxy, cyano or phenyl; by reacting nitriles with succinic esters or lactams or enamines in an alkaline medium to give a pigment alkali salt and subsequent protolysis of the pigment alkali metal salt, characterized in that an effective amount of a pigment dispersant of the formula (II) is added during the protolysis of the pigment alkali metal salt
• Q is a residue of an organic pigment from the group of perinone, quinacridone, quinacridonequinone, anthanthrone, indanthrone, dioxazine, such as triphendioxazines, diketopyrrolopyrrole, indigo, thioindigo, thiazineindigo, isoindoline, isoindolinone Pyranthrone, isoviolanthrone, flavanthrone or anthrapyrimidine pigments; s is a number from 1 to 5, preferably 1 to 3; n represents a number from 0 to 4, preferably 0.1 to 2; wherein the sum of s and n is 1 to 5;
• R J is a branched or unbranched, saturated or unsaturated, aliphatic hydrocarbon radical having 1 to 20 C atoms, or a C 5 -C 7 cycloalkyl radical, or an araliphatic or aromatic radical having 1, 2 or 3 aromatic rings, the rings condensing or a heterocyclic radical having 1, 2 or 3 rings containing 1, 2, 3 or 4 heteroatoms from the group O, N and S, or a combination thereof; wherein said hydrocarbon, cycloalkyl, aromatic, Araliphaten- and heteroaromatic radicals by 1, 2, 3 or 4 substituents selected from the group OH, CN, F, Cl, Br, NO 2 , CF 3 , CrC 6 alkoxy , C 1 -C 6 -alkyl, NHCONH 2 , NHC (NH) NH 2 , NHCO-C 1 -C 6 -alkyl, C 1 -C 6 -alkyl, COOR 5 , CONR 5 R 6 ,
• E + , G + are independently H + or the equivalent M p + / m of a metal cation
• E + and / or G + represent an ammonium ion
• the substituents R 7 , R 8 , R 9 and R 10 are each independently of one another a hydrogen atom, C 1 -C 6 -alkyl, C 2 -C 3 o-alkenyl, C 5 -C 3 o-cycloalkyl, phenyl, (C 1 -C 8 ) -alkylphenyl, (C 1 -C 4 ) -alkylene-phenyl, or a ( Poly) alkyleneoxy group of the formula - [CH (R 11 ) -CH (R 11 ) -O] k -H, in which k is a number from 1 to 30 and the two radicals R 11 independently of one another are hydrogen, C 4 alkyl or, when k> 1, a combination thereof; and wherein R 7 , R 8 , R 9 and / or
• R 12 , R 13 , R 14 and R 15 are independently hydrogen or a
• T is a branched or unbranched C 2 -C 6 -alkylene radical; or wherein T, when q> 1, may also be a combination of branched or unbranched C 2 -C 6 -alkylene radicals.
• Q is a residue of an organic pigment from the group of the quinacridone
• R 3 is C 1 -C 6 -alkyl, benzyl, phenyl, each of which is substituted by 1, 2, 3 or 4 substituents from the group OH, C 1 -C 6 -alkoxy, SC 1 -C 6 -alkyl, NHCONH 2 ,
• R 5 and R 6 are the same or different and are hydrogen, phenyl or
• R 4 is hydrogen
• E + , G + is hydrogen, an alkaline earth metal or an alkali metal or a metal of the third main group, in particular Li, Na, K, Ca, Sr, Ba, Al or an ammonium ion.
• pigment dispersants of the formula (II) Q is a radical of an organic pigment from the group of
• Diketopyrrolopyrrole pigments preferably the PR 255 or the PR 264 R 3 CrC 6 alkyl, represented by 1, 2, 3 or 4 substituents from the group
• R 4 is hydrogen
• E + is hydrogen
• G + is hydrogen, an alkaline earth metal or an alkali metal or a metal of the third main group, in particular Li, Na, K, Ca, Sr, Ba, Al or an ammonium ion.
• the pigment dispersants of formula (II) are compounds known per se and can be prepared by known methods, e.g. according to EP-A-1 104 789, JP 03026767 or WO 02/064 680.
• R 1a and R 2a are identical or different and are hydrogen, methyl, tert-butyl, chlorine, cyano or phenyl.
• Examples of preferred pigments of formula (I) are Cl. Pigment Orange 71, 73, 81, Pigment Red 254, 255, 264, 270, 272.
• a preferred embodiment of the method according to the invention is characterized by reacting 1 mol of a succinic acid dicyclohexyl, dialkyl ester, -monoalkylmonophenylesters, or diphenyl, wherein the succinic acid alkyl radical d-Ci 8 alkyl and phenyl unsubstituted or substituted by one or two alkyl CrC ⁇ or C r C 6 alkoxy groups substituted phenyl, with 2 moles of a mixture of nitriles of the formulas R 1a R 1b C 6 H 3 -CN and R 2a R 2b C 6 H 3 -CN, wherein R 1a , R 1b , R 2a and 2b have the abovementioned meaning, wherein in the nitrile mixture R 1a R 1b C 6 H 3 -CN and R 2a R 2b C 6 H 3 -CN in a molar ratio of 100: 0 to 50:50 to each other; or by reacting
• R 1a , R 1b , R 2a and R 2b have the meaning given above and R 1c and R 1d are alkyl or aryl, preferably C 1 -C 8 -AlkVl or C 6 -C 0 -ArVl, mean; in an inert organic solvent in the presence of an alkali metal or an alkali metal alcoholate as a strong base at elevated temperature to give a pigment alkali salt, followed by protolysis of a compound of the formula (I), characterized in that the pigment alkali salt and a pigment dispersant of the formula (II) in a liquid protolysis medium, or the pigment alkali metal salt is added to a liquid protolysis medium in which a pigment dispersant of the formula (II) is dissolved or suspended, and wherein the amount of pigment dispersant of the formula (II) added is at least 0.05% by weight ,
• Suitable acids are, for example, aliphatic or aromatic carboxylic or sulphonic acids, such as, for example, formic acid, acetic acid, propionic acid, oxalic acid, Benzoic acid or benzenesulfonic acid.
• mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.
• neutral water a mixture of methanol and water or water at pH ⁇ 5.
• the weight ratio of pigment of the formula (I) to the pigment dispersant of the formula (II) is preferably between (99.9 to 0.1) and (80 to 20), more preferably between (97 to 3) and (83 to 17) and most preferably between (95 to 5) and (85 to 15).
• a "direct" preparation of finely divided pigments means that the pigments obtained from the process according to the invention are already sufficiently finely divided and also readily dispersible and no longer require a subsequent comminution step EP-A- 0 962 499.
• the protolysis in the presence of the pigment dispersant (II) is expediently carried out at a temperature of the pigment alkali salt of 20 to 120 ° C., preferably 40 to 90 ° C.
• the liquid protolysis medium preferably has a temperature of 0 to 60 0 C, in particular 0 to 30 0 C.
• the amount of protolysis medium must be such that complete protolysis of the pigment alkali salt and the alcoholate used is ensured. Appropriately, one works in a larger excess of Protolysemedium.
• auxiliaries or additives may be added in the course of the process according to the invention or following, for example surfactants, dispersants, fillers, setting agents, resins, waxes, defoamers, antidusting agents, extenders, antistatic agents, preservatives, drying retardants, wetting agents, antioxidants, UV stabilizers.
• Absorber and light stabilizers preferably in an amount of 0.1 to 10 wt .-%, in particular 0.5 to 5 wt .-%, based on the total weight of the pigment.
• Suitable surfactants are anionic or anionic, cationic or cationic and nonionic or amphoteric substances or mixtures of these agents.
• surfactants may be the classes of compounds described in International Application PCT / EP 2006/008866.
• the pigment preparation produced according to the invention can be used as preferably aqueous presscake, dry powder or dry granules, but as a rule they are solid systems of powdery nature.
• drying units When drying a wet pigment preparation, the known drying units can be used, such as drying cabinets, paddle wheel dryers, tumble dryers, contact dryers and in particular spinflash and spray dryers.
• the pigment preparations prepared according to the invention are distinguished by their excellent coloristic and rheological properties, in particular high flocculation stability, easy dispersibility, good rheology, high color strength, transparency and saturation (chroma). They are in many
• pigment dispersions show excellent rheological properties even with high pigmentation of the coating or printing ink concentrates. Other properties, such as gloss, overcoating fastness, solvent fastness, alkali and acid fastness, light and weather fastness and high purity of hue, are very good.
• hues in the red range which are required when used in color filters can be achieved. Here they ensure high contrast and also satisfy the other requirements imposed on color filters, such as high temperature stability or steep and narrow absorption bands.
• the half-width of the pigments according to the invention is preferably 40 to 100 nm, in particular 50 to 85 nm.
• the pigment preparations according to the invention can be used in principle for pigmenting all high molecular weight organic materials of natural or synthetic origin, for example of plastics, resins, paints, especially metallic paints, paints, electrophotographic toners and developers, electret materials, color filters and inks, printing inks.
• the pigment preparations prepared according to the invention are suitable as colorants in aqueous-based and non-aqueous-based ink-jet inks and in inks which operate according to the hot-melt method.
• the pigment preparations prepared according to the invention are also colorants for color filters, both for additive and for subtractive color generation, such as in electro-optical systems such as television screens, LCD (liquid crystal displays), charge coupled devices, plasma displays or electroluminescent displays, which in turn can be active (twisted nematic) or passive (supertwisted nematic) ferroelectric displays or light-emitting diodes, as well as colorants for electronic inks ("e-inks”) or "electronic paper” (“e paper ").
• electro-optical systems such as television screens, LCD (liquid crystal displays), charge coupled devices, plasma displays or electroluminescent displays, which in turn can be active (twisted nematic) or passive (supertwisted nematic) ferroelectric displays or light-emitting diodes, as well as colorants for electronic inks ("e-inks”) or "electronic paper” ("e paper ").
• a stable paste or a pigmented photoresist also has a high pigment purity
• the pigmented color filters can also be applied by ink jet printing or other suitable printing methods.
• the red shades of the pigment preparations according to the invention are particularly well suited for the Color Filter Red-Green-Blue color set (R 1 G 1 B). These three colors are present as separate color dots side by side, and result from backlit a full color image.
• Typical colorants for the red color point are pyrrolopyrrole, quinacridone and azo pigments, e.g. Cl. Pigment Red 254, Cl. Pigment Red 209, Cl. Pigment Red 175 and Cl. Pigment Orange 38, single or mixed.
• phthalocyanine colorants are typically used, e.g. Cl. Pigment Green 36 and Cl. Pigment Green 7. If required, additional colors can be added to the respective color dots for nuancing.
• For the red and green hue is preferably mixed with yellow, for example with Cl. Pigment Yellow 138, 139, 150, 151, 180 and 213.
• the pigments obtained were completely dispersed in an alkyd melamine lacquer system and the frequency distribution of the crystalline particles in this lacquer system was determined with the aid of a disk centrifuge.
• a density gradient was set in the spin fluid of the disk centrifuge.
• the density gradient was through Mixture of 40 to 60 wt .-% XyIoI set with the above-mentioned paint base of alkyd melamine paint system.
• the disodium salt of the pigment obtained by this process is converted into the pigment by hydrolysis of the cooled to 80 0 C hot disodium salt suspension by discharging to 420 parts of neutral water.
• the disodium salt of the pigment obtained by this process is converted by hydrolysis of the cooled to 80 0 C hot disodium salt suspension by discharging to 420 parts of neutral 40 0 C water in the pigment. After isolation and washing with methanol and water, a pigment is obtained which has a maximum of the frequency distribution (the mode of distribution) of the crystalline particles of 190 nm.
• the BET surface area of the pigment is 81 m 2 / g.
• the disodium salt of the pigment obtained by this process is converted into the pigment by hydrolysis of the cooled to 80 0 C hot disodium salt suspension by discharging to 420 parts of neutral water.
• a pigment After isolation and washing with methanol and water, a pigment is obtained which has a maximum of the frequency distribution (the mode of distribution) of the crystalline particles of 140 nm.
• the BET surface area of the pigment is 88 m 2 / g.
• the pigment is prepared analogously to Comparative Example 1, except that the disodium salt of the pigment is converted into the pigment by hydrolysis of the 80 ° C. disodium salt suspension by discharging to 420 parts of neutral water in which 3.7 parts of the pigment dispersant (VI) are dispersed becomes. After isolation and washing with methanol and water to obtain a pigment which is a maximum of the frequency distribution (the mode of distribution) of has crystalline particles of 79 nm and a half-width of the frequency distribution of 58 nm.
• the BET surface area of the pigment is 130 m 2 / g.
• the pigment is prepared analogously to Example 1, wherein 1, 8 parts of the
• Pigment dispersant (VI) are dispersed in water.
• the BET surface area of the pigment is 100 m 2 / g.
• Example 3 The pigment is prepared analogously to Example 1, with 3.7 parts of the pigment dispersant (VII) being dispersed in the water.
• the BET surface area of the pigment is 107 m 2 / g.
• the pigment is prepared analogously to Example 3, wherein 1, 8 parts of the
• Pigment dispersant (ViI) are dispersed in water.
• Frequency distribution of 89 nm has.
• the BET surface area of the pigment is 93 m 2 / g.
• the pigment is prepared analogously to Example 1, with 3.7 parts of the
• Pigment dispersant (VIII) are dispersed in water.
• the BET surface area of the pigment is 95 m 2 / g.
• the pigment is prepared analogously to Example 5, wherein 1, 8 parts of the
• Pigment dispersant (VIII) are dispersed in water.
• the BET surface area of the pigment is 91 m 2 / g.
• the pigment is prepared analogously to Example 1, with 3.7 parts of the
• Pigment dispersant (IX) are dispersed in water.
• the BET surface area of the pigment is 115 m 2 / g.
• the pigment is prepared analogously to Example 7, wherein 1, 8 parts of the
• Pigment dispersant (IX) are dispersed in water.
• the BET surface area of the pigment is 107 m 2 / g.
• the pigment is prepared analogously to Example 1, with 3.7 parts of the
• Pigment dispersant (X) are dispersed in water.
• the BET surface area of the pigment is 85 m 2 / g.
• the pigment is prepared analogously to Example 1, with 3.7 parts of the
• Pigment dispersant (Xl) are dispersed in water.
• the BET surface area of the pigment is 124 m 2 / g.
• the pigment is prepared analogously to Example 10, wherein 1, 8 parts of the
• Pigment dispersant (Xl) are dispersed in water.
• the pigment is prepared analogously to Example 1, wherein the disodium salt of the pigment is converted into the pigment by hydrolysis of the 80 ° C. disodium salt suspension by discharging to 420 parts of neutral water in which 3.7 parts of the pigment dispersant (V) are present , After isolation and washing with methanol and water to obtain a pigment having a maximum of the frequency distribution (the mode of distribution) of the crystalline particles of 125 nm and a half-width of the frequency distribution of 94 nm.
• the BET surface area of the pigment is 92 m 2 / g.
• the pigment is prepared analogously to Example 12, wherein 1, 8 parts of the
• Pigment dispersant (V) are dispersed in water. After isolation and washing with methanol and water to obtain a pigment having a maximum of the frequency distribution (the mode of distribution) of the crystalline particles of 121 nm and a half-width of the
• the BET surface area of the pigment is 91 m 2 / g.
• Example 12 -IV much more transparent

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• Ink Jet Recording Methods And Recording Media Thereof (AREA)

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• 2007
  • 2007-03-07 DE DE102007011068A patent/DE102007011068A1/de not_active Withdrawn
• 2008
  • 2008-02-20 EP EP08715877A patent/EP2134793B1/de not_active Not-in-force
  • 2008-02-20 CN CN200880004660XA patent/CN101616999B/zh not_active Expired - Fee Related
  • 2008-02-20 WO PCT/EP2008/001306 patent/WO2008107073A1/de active Application Filing
  • 2008-02-20 JP JP2009552088A patent/JP5340178B2/ja not_active Expired - Fee Related
  • 2008-02-20 US US12/530,094 patent/US7967906B2/en not_active Expired - Fee Related
  • 2008-02-20 ES ES08715877T patent/ES2388195T3/es active Active

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